Olefin oligomerization by main group Ga3+ and Zn2+ single site catalysts on SiO2

Abstract

In heterogeneous catalysis, olefin oligomerization is typically performed on immobilized transition metal ions, such as Ni²⁺ and Cr³⁺. Here we report that silica-supported, single site catalysts containing immobilized, main group Zn²⁺ and Ga³⁺ ion sites catalyze ethylene and propylene oligomerization to an equilibrium distribution of linear olefins with rates similar to that of Ni²⁺. The molecular weight distribution of products formed on Zn²⁺ is similar to Ni²⁺, while Ga³⁺ forms higher molecular weight olefins. In situ spectroscopic and computational studies suggest that oligomerization unexpectedly occurs by the Cossee-Arlman mechanism via metal hydride and metal alkyl intermediates formed during olefin insertion and β-hydride elimination elementary steps. Initiation of the catalytic cycle is proposed to occur by heterolytic C-H dissociation of ethylene, which occurs at about 250 °C where oligomerization is catalytically relevant. This work illuminates new chemistry for main group metal catalysts with potential for development of new oligomerization processes.

Silica-supported, single site, main group Zn(II) and Ga(III) ions catalyze ethylene and propylene oligomerization. Here, experimental and theoretical evidence suggests a Cossee-Arlman reaction mechanism similar to that for transition metal catalysts.